CN102897786B - Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent - Google Patents
Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent Download PDFInfo
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Abstract
The invention relates to a synthesis method for hierarchically porous ZIF-8 and a preparation method for deep desulfurizing agent. The method includes the following steps: 2-methylbenzimidazole is dissolved in sulfuric acid, the concentration of which is 98 wt percent, hydrogen peroxide, the concentration of which is 30 wt percent, is then dripped, the solution is heated to a certain temperature and refluxed under constant temperature for 2 to 5 hours after dripping, the reaction solution is poured into ice water and recrystallized, and product is separated out, washed and dried, so that 2-methylimidazole-4, 5-dicarboxylic acid is obtained; the 2-methylimidazole-4, 5-dicarboxylic acid as ligand, template and sodium hydroxide are dissolved into deionized water, uniformly mixed and then added with zinc source, and after agitation, mixed solution is obtained; the mixed solution is crystallized, and solid product is then separated out, washed and dried, so that ZIF-8 raw powder is obtained; with organic solvent as extracting agent, the template in the ZIF-8 is extracted out, and thereby the hierarchically porous ZIF-8 is obtained. The invention also provides the method for preparing the deep desulfurizing agent by utilizing the hierarchically porous ZIF-8. The hierarchically porous ZIF-8 synthesized by the method has the characteristics of high external specific surface area and high pore volume.
Description
Technical field
The present invention relates to the preparation method of a kind of multistage pore canal class ZIF-8 and the preparation method of deep desulfurization absorbent, belong to porous material and petroleum catalyst technical field.
Background technology
The crystalline material that metallic organic framework (MOFs) is comprised of organic ligand connection metal ion or metal cluster.Because they have larger surface-area and permanent duct, MOFs has caused great attention in recent years.Research shows, MOFs material has very large application potential aspect absorption, gas storage, sensor, catalysis.Although MOFs material has very large specific surface area, their micropore (aperture < 2nm) has limited macromolecular diffusion and absorption, has limited its application with aspects such as separated, catalysis at macromolecules adsorption.
At present, in order to improve the performance of MOFs, the successful example of the mesoporous MOFs material of more existing synthetic aperture scopes in 2-50nm.For example, MIL-101, UMCM-2 and PCN-105 are because it has the performance that cage in mesoporous scope has mesoporous material; Yet, the inside that macromolecular structure has been limited in the duct in non-mesoporous scope.Select longer organic ligand also can obtain mesoporous MOFs material, but except a few, major part is easily caved in or directly form chain-like structure by the synthetic MOFs material structure after removing guest molecule of long part.
As multi-stage pore canal molecular sieve, there is micropore and mesoporous material has very strong using value in many aspects simultaneously, as drug release, gas storage, separation and catalysis aspect, this is that mesoporous and performance micropore are incorporated in to the advantage on commaterial.The preparation of step hole MOFs material is the problem that first will solve, at present, and the example that only has multistage pore canal MOFs few in number to prepare.The people such as Zhang (Zhao Y, Zhang J, Han B, Song J, Li J, Wang Q.Metal-Organic Framework Nanospheres with Well-Ordered Mesopores Synthesized in an Ionic Liquid/CO
2/ Surfactant System.Angewandte Chemie International Edition, 2011; 50 (3): 636-639.) at ionic liquid/CO
2in/surfactant system, take zinc nitrate hexahydrate as source metal, and the terephthalic acid of take has order mesoporous MOFs material as part has successfully synthesized.The people such as the Qiu Lingguang of University of Anhui (Qiu L-G, Xu T, Li Z-Q, Wang W, Wu Y, Jiang X, Tian X-Y, Zhang L-D.Hierarchically Micro-and Mesoporous Metal-Organic Frameworks with Tunable Porosity..Angewandte Chemie International Edition, 2008; 47 (49): 9487-9491.) take CTAB as template, successfully synthesized the HKUST-1 of multistage pore canal, obtained having simultaneously and enriched micropore and mesoporous MOFs material.The people such as Do (Pham M-H, Vuong G-T, Fontaine F-G, Do T-O.A Route to Bimodal Micro-Mesoporous Metal-OrganicFrameworks Nanocrystals.Crystal Growth & Design, 2012; 12 (2): 1008-1013.) take nonionic surface active agent F127 as template, with solvent-thermal method, also obtained the HKUST-1 of multistage pore canal.But because the thermostability of MOFs is lower, and responsive to electronic water, Qiu Lingguang and Do fail to obtain transmission electron microscope picture clearly, and this stability that MOFs is also described is lower, and this also can limit its application potential undoubtedly.
As the Yi Ge branch of MOFs, ZIFs material is just receiving increasing concern because of its unique class zeolite crystal structure and high thermal stability and chemical stability.Wherein, the thermostability of ZIF-8 can reach 550 ℃, is that most of MOFs material is incomparable.And the outside surface of ZIF-8 has acid-alkali active sites, can be used as heterogeneous catalyst or sorbent material.Although ZIF-8 has very high specific surface area (900-1600m
2/ g), but its external surface area is but not high, and its acid-alkali active sites exists only in outside surface, and this has just limited putting to good use of its catalysis and absorption property.Although can look like the synthetic example of multistage pore canal MOFs, adopt cats product to synthesize multistage pore canal ZIF-8 to improve its external surface area as template, but the part glyoxal ethyline of ZIF-8 is after being attracted by micella, due to electrostatic interaction, metal ion is difficult to react near micella, thereby is difficult to synthetic multistage pore canal ZIF-8.
Summary of the invention is pressed
In order to solve the problems of the technologies described above, the object of the present invention is to provide the preparation method of a kind of multistage pore canal class ZIF-8, by the part of anamorphic zone carboxyl, take cats product as template, synthesize the multistage pore canal class ZIF-8 of high external surface area, high pore volume.
The present invention also aims to provide a kind of preparation method of deep desulfurization of gasoline sorbent material.
For achieving the above object, first the present invention provides the preparation method of a kind of multistage pore canal class ZIF-8, and it comprises the following steps:
2-tolimidazole is dissolved in the sulfuric acid that 70-80 ℃ of concentration is 98wt%, then drip the hydrogen peroxide solution that concentration is 30wt%, after dropwising, rise to 100-130 ℃ of constant temperature backflow 2-5 hour, pour reaction solution in frozen water recrystallization, separated product, washing, dry glyoxal ethyline-4 that obtain, 5-dicarboxylic acid, wherein, the mass ratio of 2-tolimidazole, sulfuric acid, hydrogen peroxide solution is 1: 15-18: 7-9;
By glyoxal ethyline-4,5-dicarboxylic acid is dissolved in deionized water as part, template, sodium hydroxide, adds zinc source after mixing, and stirs and obtains mixing solutions; Wherein, described zinc source, glyoxal ethyline-4, the mol ratio of 5 dicarboxylic acid, template, sodium hydroxide, deionized water is 1: 3-6: 0.62-2.03: 127-156: 100-204;
Mixing solutions is carried out to crystallization, and then solid product is separated, washing, dry, obtains the former powder of class ZIF-8;
Take organic solvent as extraction agent extracts the template in the former powder of class ZIF-8, obtain multistage pore canal class ZIF-8.
In the preparation method of above-mentioned multistage pore canal class ZIF-8, preferably, the template adopting is cetyl trimethylammonium bromide (CTAB) etc.
In the preparation method of above-mentioned multistage pore canal class ZIF-8, preferably, the zinc source adopting is zinc nitrate hexahydrate and/or zinc acetate etc.
In the preparation method of above-mentioned multistage pore canal class ZIF-8, preferably, the temperature of the stirring before crystallization is 50-60 ℃, and churning time is 20-40 minute, adds the stirring afterwards of zinc source.
In the preparation method of above-mentioned multistage pore canal class ZIF-8, preferably, the temperature of crystallization is 120-140 ℃, and crystallization time is 20-26 hour.
In the preparation method of above-mentioned multistage pore canal class ZIF-8, preferably, the extraction agent adopting is dehydrated alcohol, and extraction temperature is 50-60 ℃, and every gram of former powder of class ZIF-8 extracts with the dehydrated alcohol of 70-100mL, and extraction time is 10-15 hour.
Preparation method provided by the invention be take cats product as template, and the imidazole derivative of take with carboxyl is part, the synthetic multistage pore canal class ZIF-8 simultaneously with micropore, mesoporous, macropore, and it has higher external surface area and pore volume.Take cats product during as template, and template concentration can form micella after surpassing micelle-forming concentration in solution, and micellar surface is positively charged.Adding of sodium hydroxide can make the micelle-forming concentration of cats product reduce, micella increases, and adds after the imidazole derivative with carboxyl in this solution, electronegative after carboxyl deprotonation, by electrostatic interaction and micella, attract each other, be gathered in micellar surface; Add again after source metal, the N atom generation coordination reaction on source metal and imidazole derivative, micella has served as mesoporous template, generates multistage pore canal class ZIF-8.Carrying out along with reaction, there will be phase-splitting, and cats product serves as the template of macropore mutually, causes the formation of macropore.By regulate cats product add-on number, can control mesoporous and porosity macropore.
The present invention also provides a kind of preparation method of deep desulfurization of gasoline agent, and it comprises the following steps:
According to the preparation method of above-mentioned multistage pore canal class ZIF-8, prepare multistage pore canal class ZIF-8;
Multistage pore canal class ZIF-8 is scattered in the solution of inorganic salt of copper, the ratio of the two is 1g: 100mL, stirs, and dry, roasting obtains the multistage pore canal class ZIF-8 (Cu/ multistage pore canal class ZIF-8) of supported copper, i.e. deep desulfurization of gasoline agent.
In the preparation method of above-mentioned deep desulfurization of gasoline agent, preferably, the inorganic salt of the copper adopting are ventilation breather etc.
In the preparation method of above-mentioned deep desulfurization of gasoline agent, preferably, the solution of the inorganic salt of the copper that adopts is the ammonia soln of the ventilation breather of concentration 0.010-0.015mol/L, and the concentration of preparing the ammoniacal liquor that this solution adopts is 25-28wt%.
In the preparation method of above-mentioned deep desulfurization of gasoline agent, preferably, whipping temp is 30-60 ℃, and churning time is 2-6h; Maturing temperature is 200-400 ℃, and roasting time is 2-6h, and the atmosphere of roasting is N
2atmosphere, N
2flow velocity is 10-30mL/min.
The synthetic multistage pore canal class ZIF-8 of the present invention has the structure identical with ZIF-8, has abundant microvoid structure, and the introducing of mesoporous and macropore, has enriched its pore passage structure especially.After supported copper, form the adsorption activity position to sulfocompound.The multistage pore canal class ZIF-8 preparing due to the present invention has abundant mesoporous and macropore, can significantly improve the diffusion mass transfer of sulfocompound in sorbent material, improves the adsorption effect to sulfocompound.
Accompanying drawing explanation
Fig. 1 is embodiment 1-4 and the class ZIF-8 of comparative example 1 synthesized and the X-ray diffractogram of ZIF-8;
Fig. 2 is the nitrogen adsorption desorption result figure of class ZIF-8 and the ZIF-8 of embodiment 1 and comparative example 1 synthesized;
Fig. 3 is the transmission electron microscope picture of the class ZIF-8 of embodiment 1 synthesized;
Fig. 4 is the scanning electron microscope picture of the class ZIF-8 of embodiment 2 synthesizeds.
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, referring now to Figure of description, technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
The present embodiment provides the preparation method of a kind of multistage pore canal class ZIF-8, and it is to take CTAB as template, with glyoxal ethyline-4, and 5-dicarboxylic acid synthesizes multistage pore canal class ZIF-8 material, comprises the following steps:
With graduated cylinder, measure the 100mL vitriol oil (98wt%) and be placed in 500mL beaker, beaker is placed in to 80 ℃ of water-baths; 10g 2-tolimidazole is added in above-mentioned beaker and dissolved under strong stirring; Measure 100mL concentration and be 30% hydrogen peroxide, be placed in separating funnel, in above-mentioned solution, slowly drip; After dropwising, solution is poured in the round-bottomed flask of 500mL, temperature is risen to 100 ℃, stirring and refluxing 3h; Then, solution is poured in 200mL frozen water, standing crystallize out, suction filtration separated product, is neutral with deionized water wash to filtrate, and 40 ℃ of dry 24h, obtain glyoxal ethyline-4,5-dicarboxylic acid;
1g CTAB is dissolved in 50mL deionized water, adds wherein 9gNaOH, be stirred to its dissolving; In solution, add above-mentioned glyoxal ethyline-4 of 0.9g, 5-dicarboxylic acid, is stirred to its dissolving; Add again 0.524g Zn (NO
3)
23H
2o, in 55 ℃ of stirred in water bath 30min; Above-mentioned solution is placed in to 100mL tetrafluoroethylene reactor, and crystallization 24h at 140 ℃, obtains the former powder of multistage pore canal class ZIF-8;
Get the former powder of 1g multistage pore canal class ZIF-8 and be placed in 250mL round-bottomed flask, add wherein 100ml dehydrated alcohol, stirring and refluxing 12h under 60 ℃ of water bath condition; Suction filtration separated product, uses absolute ethanol washing 3 times, and 100 ℃ of dry 12h, obtain multistage pore canal class ZIF-8.
The present embodiment also provides a kind of preparation method of deep desulfurization absorbent, and it comprises the following steps:
1g multistage pore canal class ZIF-8 is scattered in the ammonia soln that 100mL concentration is the ventilation breather of 0.013mol/L (preparing the ammonia concn that this solution adopts is 25-28wt%), and 60 ℃ are stirred 2h, dry after in 200 ℃, N
2roasting 2h under atmosphere, N
2flow velocity is 20mL/min, obtains Cu/ multi-stage porous class ZIF-8, i.e. deep desulfurization absorbent.
The X-ray diffraction spectrogram of multistage pore canal class ZIF-8 prepared by the present embodiment is as shown in the curve B in Fig. 1, and pore structure data are as shown in table 1, and nitrogen adsorption desorption result is as shown in the curve B in Fig. 2, and transmission electron microscope photo as shown in Figure 3.
Comparative example 1
This comparative example provides the preparation method of a kind of conventional ZIF-8, and it is to take glyoxal ethyline as the synthetic conventional ZIF-8 of part, comprises following concrete steps:
0.579g glyoxal ethyline is dissolved in 50mL deionized water, adds wherein 0.524g Zn (NO
3)
26H
2o dissolves; To dripping n-Butyl Amine 99 in above-mentioned solution, regulate pH value to 10.0 left and right, and stir 30min under 55 ℃ of water-baths; Above-mentioned solution is placed in to 100mL tetrafluoroethylene reactor, in 140 ℃ of crystallization 24h; Suction filtration separated product, uses deionized water wash 3 times, and 100 ℃ of dry 12h, obtain conventional ZIF-8.
This comparative example also provides a kind of preparation method of deep desulfurization absorbent, and it comprises the following steps:
The conventional ZIF-8 of 1g is scattered in the ammonia soln that 100mL concentration is the ventilation breather of 0.013mol/L (preparing the ammonia concn that this solution adopts is 25-28wt%), and 60 ℃ are stirred 2h, dry after in 200 ℃, N
2roasting 2h under atmosphere, N
2flow velocity is 20mL/min, obtains the conventional ZIF-8 of Cu/.
The X-ray diffraction spectrogram of this routine ZIF-8 is as shown in the curve A in Fig. 1, and pore structure data are as shown in table 1, and nitrogen adsorption desorption result is as shown in the curve A in Fig. 2.
Embodiment 2
The present embodiment provides the preparation method of a kind of multistage pore canal class ZIF-8, it is on the basis of embodiment 1, to improve CTAB consumption, synthetic multistage pore canal class ZIF-8, particularly: change the 1g CTAB in embodiment 1 into 1.3g CTAB, remaining reaction thing composition and operational condition are identical with embodiment 1.
The X-ray diffraction spectrogram of this multistage pore canal class ZIF-8 is as shown in the curve C in Fig. 1, and nitrogen adsorption desorption result is as shown in the curve C in Fig. 2, and pore structure data are as shown in table 1, and scanning electron microscope picture as shown in Figure 4.
Embodiment 3
The present embodiment provides the preparation method of a kind of multistage pore canal class ZIF-8, it is on the basis of embodiment 1, to reduce CTAB consumption, synthetic multistage pore canal class ZIF-8, particularly: change the 1g CTAB in embodiment 1 into 0.7g CTAB, remaining reaction thing composition and operational condition are identical with embodiment 1.
The X-ray diffraction spectrogram of this multistage pore canal class ZIF-8 is as shown in the curve D in Fig. 1, and nitrogen adsorption desorption result is as shown in the curve D in Fig. 2, and pore structure data are as shown in table 1.
Embodiment 4
The present embodiment provides the preparation method of a kind of multistage pore canal class ZIF-8, it is on the basis of embodiment 1, to reduce CTAB consumption, synthetic multistage pore canal class ZIF-8, particularly: change the 1g CTAB in embodiment 1 into 0.4g CTAB, remaining reaction thing composition and operational condition are identical with embodiment 1.
The X-ray diffraction spectrogram of this multistage pore canal class ZIF-8 is as shown in the curve E in Fig. 1, and nitrogen adsorption desorption result is as shown in the curve E in Fig. 2, and pore structure data are as shown in table 1.
Data from table 1 can be found out, compare with conventional ZIF-8, use cats product do template, with glyoxal ethyline-4,5-dicarboxylic acid be the multistage pore canal class ZIF-8 of part synthesized when retaining microvoid structure, also there is larger external surface area and pore volume.Use cats product to be the resulting class ZIF-8 of template, its micropore surface is long-pending almost identical with conventional ZIF-8, but external surface area and pore volume all have significant improvement.By the consumption of adjusting template agent, can regulate within the specific limits the external surface area of class ZIF-8.
From XRD spectra (Fig. 1), can find out, with glyoxal ethyline-4, the class ZIF-8 that 5-dicarboxylic acid is part, the cats product of take is template synthesized has identical XRD spectra with conventional ZIF-8, and this illustrates that it has identical crystalline structure.From nitrogen adsorption-desorption curve (Fig. 2), can find out, compare nitrogen adsorption-desorption curve with the class ZIF-8 of method synthesized of the present invention with conventional ZIF-8 and have and significantly return stagnant ring, illustrate that the multi-stage porous class ZIF-8 of synthesized of the present invention has mesoporous existence.From transmission electron microscope photo (Fig. 3), can find out, black part is divided into class ZIF-8, at black partly distributing high-density white or gray corrosion, the mesoporous and macropore that Here it is in class ZIF-8 crystal.As shown in Figure 3, white dot is not of uniform size, and widely dispersed has also having in mesoporous scope (2-50nm) (> 50nm) within the scope of macropore.
The pore structure parameter of the class ZIF-8 that table 1 embodiment 1-4 and comparative example 1 are synthetic
Performance evaluation
Performance to deep desulfurization of gasoline sorbent material is evaluated, and according to following steps, carries out:
The octane that is dissolved with thiophene of take is model gasoline, and embodiment 1-4 and the prepared Cu/ class ZIF-8 of comparative example 1 are carried out to adsorption desulfurize performance evaluation.Appreciation condition is: 35 ℃ of temperature of reaction, reaction pressure normal pressure, agent-oil ratio 1: 5, Static Adsorption.Evaluation result is as shown in table 2.
Table 2 model gasoline is at the adsorption desulfurize reaction result of Cu/ multi-stage porous ZIF-8
| Sorbent material | Initial sulphur content (μ g/g) | Sulphur content (μ g/g) after absorption | Desulfurization degree (%) |
| Comparative example 1 | 250 | 110.12 | 55.95 |
| Embodiment 1 | 250 | 33.45 | 86.62 |
| Embodiment 2 | 250 | 27.73 | 88.91 |
| Embodiment 3 | 250 | 25.00 | 90.00 |
| Embodiment 4 | 250 | 22.20 | 91.12 |
From table 2, the data of evaluation result can be found out, according to the Cu/ multistage pore canal class ZIF-8 of synthetic method synthesized provided by the invention, all than the conventional ZIF-8 of Cu/, have higher desulfurization degree.The surface of class ZIF-8 has incomplete glyoxal ethyline-4 of coordination, 5-dicarboxylic acid, and the carboxyl on part is for participating in coordination, exposed at surperficial part by carboxyl or other not group effect of coordination, make Cu be carried on the surface of class ZIF-8, by roasting, obtain the multistage pore canal class ZIF-8 of high-dispersion load copper.Multistage pore canal class ZIF-8 is more conducive to the dispersion of supported copper than conventional ZIF-8, thereby has effectively promoted the absorption of sulfocompound.Therefore, the Cu/ multi-stage porous ZIF-8 of synthesized of the present invention has more excellent gasoline desulfur effect than the conventional ZIF-8 of Cu/.
Claims (13)
1. a preparation method of multistage pore canal class ZIF-8, it comprises the following steps:
2-tolimidazole is dissolved in the sulfuric acid that 70-80 ℃ of concentration is 98wt%, then drip the hydrogen peroxide solution that concentration is 30wt%, after dropwising, rise to 100-130 ℃ of constant temperature backflow 2-5 hour, pour reaction solution in frozen water recrystallization, separated product, washing, dry glyoxal ethyline-4 that obtain, 5-dicarboxylic acid, wherein, the mass ratio of 2-tolimidazole, sulfuric acid, hydrogen peroxide solution is 1:(15-18): (7-9);
By glyoxal ethyline-4,5-dicarboxylic acid is dissolved in deionized water as part and template, sodium hydroxide, adds zinc source after mixing, and stirs and obtains mixing solutions; Wherein, described zinc source, glyoxal ethyline-4, the mol ratio of 5 dicarboxylic acid, template, sodium hydroxide, deionized water is 1:(3-6): (0.62-2.03): (127-156): (100-204), described template is cetyl trimethylammonium bromide;
Mixing solutions is carried out to crystallization, and then solid product is separated, washing, dry, obtains the former powder of class ZIF-8;
Take organic solvent as extraction agent extracts the template in the former powder of class ZIF-8, obtain multistage pore canal class ZIF-8.
2. preparation method as claimed in claim 1, wherein, described zinc source is zinc nitrate hexahydrate and/or zinc acetate.
3. preparation method as claimed in claim 1, wherein, the temperature of the stirring before described crystallization is 50-60 ℃, churning time is 20-40 minute.
4. preparation method as claimed in claim 1, wherein, the temperature of described crystallization is 120-140 ℃, crystallization time is 20-26 hour.
5. preparation method as claimed in claim 1, wherein, described extraction agent is dehydrated alcohol, extraction temperature is 50-60 ℃, the dehydrated alcohol extraction of 70-100mL for every gram of former powder of class ZIF-8, extraction time is 10-15 hour.
6. a preparation method for deep desulfurization of gasoline agent, it comprises the following steps:
2-tolimidazole is dissolved in the sulfuric acid that 70-80 ℃ of concentration is 98wt%, then drip the hydrogen peroxide solution that concentration is 30wt%, after dropwising, rise to 100-130 ℃ of constant temperature backflow 2-5 hour, pour reaction solution in frozen water recrystallization, separated product, washing, dry glyoxal ethyline-4 that obtain, 5-dicarboxylic acid, wherein, the mass ratio of 2-tolimidazole, sulfuric acid, hydrogen peroxide solution is 1:(15-18): (7-9);
By glyoxal ethyline-4,5-dicarboxylic acid is dissolved in deionized water as part and template, sodium hydroxide, adds zinc source after mixing, and stirs and obtains mixing solutions; Wherein, described zinc source, glyoxal ethyline-4, the mol ratio of 5 dicarboxylic acid, template, sodium hydroxide, deionized water is 1:(3-6): (0.62-2.03): (127-156): (100-204), described template is cetyl trimethylammonium bromide;
Mixing solutions is carried out to crystallization, and then solid product is separated, washing, dry, obtains the former powder of class ZIF-8;
Take organic solvent as extraction agent extracts the template in the former powder of class ZIF-8, obtain multistage pore canal class ZIF-8;
Multistage pore canal class ZIF-8 is scattered in the solution of inorganic salt of copper, the ratio of the two is that every gram of multistage pore canal class ZIF-8 is scattered in the inorganic salt solution of 100mL copper, stirs, dry, roasting obtains the multistage pore canal class ZIF-8 of supported copper, i.e. described deep desulfurizer.
7. preparation method as claimed in claim 6, wherein, the inorganic salt of described copper are ventilation breather.
8. the preparation method as described in claim 6 or 7, wherein, the solution of the inorganic salt of described copper is the ammonia soln of the ventilation breather of concentration 0.010-0.015mol/L, the concentration of described ammoniacal liquor is 25-28wt%.
9. preparation method as claimed in claim 6, wherein, described whipping temp is 30-60 ℃, churning time is 2-6h; Maturing temperature is 200-400 ℃, and roasting time is 2-6h, and the atmosphere of described roasting is N
2atmosphere, N
2flow velocity is 10-30mL/min.
10. preparation method as claimed in claim 6, wherein, described zinc source is zinc nitrate hexahydrate and/or zinc acetate.
11. preparation methods as claimed in claim 6, wherein, the temperature of the stirring before described crystallization is 50-60 ℃, churning time is 20-40 minute.
12. preparation methods as claimed in claim 6, wherein, the temperature of described crystallization is 120-140 ℃, crystallization time is 20-26 hour.
13. preparation methods as claimed in claim 6, wherein, described extraction agent is dehydrated alcohol, and extraction temperature is 50-60 ℃, and every gram of former powder of class ZIF-8 extracts with the dehydrated alcohol of 70-100mL, and extraction time is 10-15 hour.
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